Bimetallic catalysts nanoparticles

Formation of single-walled carbon nanotubes (SWNTs) was found to be catalyzed by metal nanoparticles [207]. Wang et al. [114] investigated bimetallic catalysts such as FeRu and FePt in the size range of 0.5-3 nm for the efficient growth of SWNTs on flat surfaces. When compared with single-component catalysts such as Fe, Ru, and Pt of similar size, bimetallic catalysts Fe/Ru and Fe/Pt produced at least 200% more SWNTs [114]. 

When the rhodium-catalyzed reaction is performed under a high pressure of CO in the presence of phosphite ligands, aldehyde products (159) are formed by insertion of CO into the rhodium-alkyl bond followed by reductive elimination (Eq. 31) [90]. The bimetallic catalysts were immobilized as nanoparticles, giving the same products and functional group tolerance, with the advantage that the catalyst could be recovered and reused without loss of... 

Ffirai and Toshima have published several reports on the synthesis of transition-metal nanoparticles by alcoholic reduction of metal salts in the presence of a polymer such as polyvinylalcohol (PVA) or polyvinylpyrrolidone (PVP). This simple and reproducible process can be applied for the preparation of monometallic [32, 33] or bimetallic [34—39] nanoparticles. In this series of articles, the nanoparticles are characterized by different techniques such as transmission electronic microscopy (TEM), UV-visible spectroscopy, electron diffraction (EDX), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) or extended X-ray absorption fine structure (EXAFS, bimetallic systems). The great majority of the particles have a uniform size between 1 and 3 nm. These nanomaterials are efficient catalysts for olefin or diene hydrogenation under mild conditions (30°C, Ph2 = 1 bar)- In the case of bimetallic catalysts, the catalytic activity was seen to depend on their metal composition, and this may also have an influence on the selectivity of the partial hydrogenation of dienes. 

Partial hydrogenation of acetylenic compounds bearing a functional group such as a double bond has also been studied in relation to the preparation of important vitamins and fragrances. For example, selective hydrogenation of the triple bond of acetylenic alcohols and the double bond of olefin alcohols (linalol, isophytol) was performed with Pd colloids, as well as with bimetallic nanoparticles Pd/Au, Pd/Pt or Pd/Zn stabilized by a block copolymer (polystyrene-poly-4-vinylpyridine) (Scheme 9.8). The best activity (TOF 49.2 s 1) and selectivity (>99.5%) were obtained in toluene with Pd/Pt bimetallic catalyst due to the influence of the modifying metal [87, 88]. 

Colloidal nanoparticles can be employed as heterogeneous catalyst precursors in the same fashion as molecular clusters. In many respects, colloidal nanoparticles offer opportunities to combine the best features of the traditional and cluster catalyst preparation routes to prepare uniform bimetallic catalysts with controlled particle properties. In general, colloidal metal ratios are reasonably variable and controllable. Further, the application of solution and surface characterization techniques may ultimately help correlate solution synthetic schemes to catalytic activity. 

The nanostructured bimetallic catalysts were characterized using several techniques, and some of the main results are summarized in this section. We first describe the size and composition of the AuPt nanoparticles determined from TEM and DCP-AES analysis. This description is followed by discussion of the phase properties based on XRD results. We further discuss the FTIR provbing of CO adsorption on the bimetallic nanoparticle catalysts. 

On the basis of the combined weight of the above results, we believe that bifunctional electrocatalytic properties may be operative for both MOR and ORR on the AuPt bimetallic nanoparticle catalysts depending on the nature of the electrolyte. For ORR in acidic electrolyte, the approaching of both the reduction potential and the electron transfer number for the bimetallic catalyst with less than 25%Pt to those for pure Pt catalyst is indicative of a synergistic effect of Au and Pt in the catalyst. For MOR in alkaline electrol)he, the similarity of both the oxidation potential and the current density for the bimetallic catalyst with less than 25%Pt to those for pure Pt catalyst is suggestive of the operation of bifunctional mechanism. Such a bifunctional mechanism may involve the following reactions ... 

How the hypothetical reaction pathway represented by Eqs. (1) to (3) may be accomphshed in a real bimetallic alloy nanoparticle Recently, Bard and co-workers discussed the possibihty to completely remove Pt from the alloy systems and proposed thermodynamic guidehnes for the design of bimetallic catalysts for dioxygen elecfroieduction. Furthermore, Wang and Balbuena... 

Heemeier M, Carlsson AF, Naschitzki M, Schmal M, Baumer M, Freund HJ (2002) Preparation and characterization of a model bimetallic catalyst Co-Pd nanoparticles supported on AI3O3. Angew Chem Int Ed 41 4073... 

Lambert reviews the role of alkali additives on metal films and nanoparticles in electrochemical and chemical behavior modihcations. Metal-support interactions is the subject of the chapter by Arico and coauthors for applications in low temperature fuel cell electrocatalysts, and Haruta and Tsubota look at the structure and size effect of supported noble metal catalysts in low temperature CO oxidation. Promotion of catalytic activity and the importance of spillover are discussed by Vayenas and coworkers in a very interesting chapter, followed by Verykios s examination of support effects and catalytic performance of nanoparticles. In situ infrared spectroscopy studies of platinum group metals at the electrode-electrolyte interface are reviewed by Sun. Watanabe discusses the design of electrocatalysts for fuel cells, and Coq and Figueras address the question of particle size and support effects on catalytic properties of metallic and bimetallic catalysts. 

From not only the scientific but the technological point of view, bimetallic nanoparticles composed of two different metal elements are of greater interest and importance than monometallic nanoparticles [7,8]. Scientists have especially focused on bimetallic nanoparticles as catalysts because of their novel catalytic behaviors affected by the second metal element added. This effect of the second metal element can often be explained in terms of an ensemble and/or a ligand effect in catalyses. Such effects appear in bimetallic catalysts composed of both zerovalent metal atoms and another metal ions [9,10]. In this case, however, metal ions do not construct nanoparticles but are located close to them to exhibit an ensemble effect. This chapter covers the bimetallic nanoparticles composed of only zerovalent metals in homogeneous systems the supported or heterogeneous systems of metal nanoparticles are not covered. 

After drying and reduction, the Pd-Ag/C catalysts are composed of bimetallic Eilloy nanoparticles ( 3 nm). CO chemisorption coupled to TEM and XRD analysis showed that that, for catalysts 1.5% wt. in each metal, the bulk composition of the alloy is close to 50% in each metal, whereas the surface is 90% in Ag and 10% in Pd [9]. Mass transfer limitations can be detected by testing the same catalyst with various pellet sizes [18]. Indeed, if the reactants diffusion is slow due to small pore sizes, the longer the distance between the pellet surface and the metal particle, the larger the influence of the difiusion rate on the apparent reaction rate. Pd-Ag catalysts with various pellet sizes were thus tested in hydrodechlorination of 1,2-dichloroethane. Results were compared to those obtained with a Pd-Ag/activated charcoal catalyst. Fig. 4 shows the evolution of the effectiveness factor of the catalysts, i.e. the ratio between the apparent reaction rate and the intrinsic reaction rate, as a function of the pellet size. The intrinsic reaction rate was considered equal to the reaction rate obtained with the smallest pellet size. When rf = 1, no diffusional limitations occur, and the catalyst works in chemical regime. When j < 1, the observed reaction rate is lower than the intrinsic reaction rate due to a slow diffusion of the reactants and products and the catalyst works in diffusional regime [18]. 

TEM micrographs of bimetallic catalysts revealed the presence of randomly accessible ordered domains as well as the partly disordered mesostructure of silica films (Figure 4). The nanoparticles of Ru-Pt have a mean size of 1.4 nm with a narrow particle size distribution (Figure 5). However, the TEM image also shows the small agglomeration of nanoparticles due to the absence of a local mesostructure. 

For bimetallic catalysts, in the equation of the model the denominator containing the coordination (adsorption) parameter is introduced, which shows a more pronounced impact of the coordination (adsorption) processes on DHL hydrogenation compared to the monometallic one. On the other hand, because the coordination (adsorption) parameter Q is very small for PdPt and PdZn nanoparticulate catalysts, the second component in the denominator can be omitted so the equation becomes W=k, i.e., identical to that found for Pd nanoparticles. Among all the catalysts, PdAu stands apart its model equation contains a squared term in the denominator [44], reveaUng the high impact of the substrate/product coordination (adsorption). 

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